CA2046634C - Copolyesters of 4,4'-biphenyldicarboxylic acid, 1, 4-butanediol and ethylene glycol - Google Patents
Copolyesters of 4,4'-biphenyldicarboxylic acid, 1, 4-butanediol and ethylene glycolInfo
- Publication number
- CA2046634C CA2046634C CA002046634A CA2046634A CA2046634C CA 2046634 C CA2046634 C CA 2046634C CA 002046634 A CA002046634 A CA 002046634A CA 2046634 A CA2046634 A CA 2046634A CA 2046634 C CA2046634 C CA 2046634C
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- Prior art keywords
- residues
- polyester
- acid
- components
- parts
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
Disclosed are polyester comprised primarily of residues of 4,4'-biphenyldicarboxylic acid, ethylene glycol and 1,4-butane-diol. Articles injection-molded from the polyesters exhibit a unique combination of properties including unusually high tensile strength and excellent heat resistance, flexural modulus and resistance to chemicals and solvents
Description
WO90/1~27 2 0 4 6 ~ 3 ~ PCT/US90/01094 COPOLYESTERS OF 4,4'-BI ~N Y ~DICARBOXYLIC
ACID, 1,4-BUTANEDIOL AND ETHYLENE GLYCOL
This invention concerns certain novel, melt-processable~poIyesters comprised primarily of residues of 4,4'-biphenyldicarboxylic acid, ethylene glycol and 1,4-butanediol. Articles injection-molded from the polyesters exhibit a unique combination of properties including unusually high tensile strength, heat resistance, and flexural modulus and excellent resistance to chemicals and solvents.
Polyesters derived from 4,4'-biphenyldicarboxylic acid and various aliphatic diols have been described generally in the literature. Polyesters comprised of residues of 4,4'-biphenyldicarboxylic acid, ethylene glycol, 1,4-butanediol and 1,6-hexanediol are disclosed by Meurisse et al, in the British Polymer Journal, 13, 57 (1981). Jackson and Morris reviewed polyesters comprised of residues of 4,4'-biphenyldicarboxylic acid and various aliphatic diols in the Journal of Applied Polymer Science, Applied Polymer Symposia, 41, 307-326 (1985). Krigbaum et al, Journal of Applied Polymer Science, Polymer Letters Edition, 20, 109-115 (1982) disclose relatively low molecular weight polyesters comprised of 4,4'-biphenyldicarboxylic acid residues -and residues derived from one of several aliphatic diols.
Polyesters containing residues of 4,4'-biphenyl-dicarboxylic acid also are disclosèd in Macromolecules, 21(1), 278-280 (1988); Polymer, 24(10), 1299-1307 (1983); Japanese Published Patent Applications (Kokai) 61-236,821 and 57-198,726; Kobunshi Ronbunshu, 44(12), 983-986 (December 1987) and U.S. Patents 2,967,266, 3,842,040, and 3,842,041. German Offenlegungsschrift 1,935,252 discloses polyesters comprised of the residues of at least two diacids such as terephthalic acid and WO ~11~27 PCT/US~/01~
2û~6~
4,4'-biphenyldicarboxylic acid and two diols such as ethylene glycol and 1,4-cyclohexanedimethanol. These known polyesters typically have inherent viscosities less than 1.2 and contain 4,4'-biphenyldicarboxylic S acid residues and usually residues of at least one additional diacid and residues of at least two diols.
U.S. Patent 4,742,151 describes generally ultra-high molecular weight polyesters having inherent viscosities greater than 1.5 comprised of diacid residues of aromatic dicarboxylic acids and diol residues of alkylene glycols of 2 to 6 carbon atoms.
The polyesters of the present invention have an inherent viscosity of at least 0.6 dl/g determined at 25C using 0.1 g of polyester per 100 mL of a solvent consisting of 25 parts by weight phenol, 35 parts by weight tetrachloroethane and 40 parts by weight p-chlorophenol and contain the following components:
A. dicarboxylic acid residues consisting of at least 80 mole percent of residues having the structure:
~ C-B. diol residues consisting of at least 90 mole percent of residues having the structure:
(1) -OCH2CH2O- and (2) -OCH2CH2CH2CH2O- and, optionally, C. dicarboxylic acid and/or diol residues, i.e., dicarboxylic acid residues, diol residues or mixtures thereof, other than components A and B, wherein the mole ratio of B(l):B(2) is about 3:1 to 0.45:1. The mole percent values set forth above are based on a total of dicarboxylic acid and diol residues of 200 percent in which the mole ratio of dicarboxylic acid residues to diol residues is 1:1, i.e., alternating repeating units of diacid and diol residues.
WO ~/1~27 PCT/US~/01~4 - 20~663~
Articles injection-molded from the polyesters of our invention possess a unique combination of high tensile strength, heat resistance, and flexural modulus.
For example, an article injection-molded from a polyester consisting only of 4,4'-biphenyldicarboxylic acid and 1,4-butanediol residues gave a tensile strength of approximately 67,571 kPa (9,800 psi). The polyester consisting only of 4,4'-biphenyldicarboxylic acid and ethylene glycol residues melts at such a high tempera-ture that it cannot be molded without encounteringsevere decomposition problems. We have found that certain of the polyesters provided by this invention can be prepared in the melt and that articles injection-molded therefrom exhibit a 2- to 3-fold increase in tensile strength, e.g., ASTM D638 tensile strengths in the range of 137,900 to 206,850 kPa (20,000 to 30,000 psi), when compared to polyester derived only from 4,4'-biphenyldicarboxylic acid and 1,4-butanediol.
The polyesters of this invention are prepared by methods generally known in the art for preparing high molecular weight polyesters by polymerizing one or more dicarboxylic acids and two or more diols, as specified hereinabove. The polyesters may be produced by direct condensation or ester interchange in the melt or in the solid phase or by a combination of these processes.
The 4,4'-biphenyldicarboxylic acid residues may be derived from the free acid or from esters such as dimethyl, diethyl, dibutyl, diphenyl, di(2-~hydroxy-ethyl)- or di(4-hydroxybutyl)-4,4'-biphenyldicarboxylate or mixtures of such esters. Up to 20 mole percent, preferably up to 10 mole percent, of the dicarboxylic acid residues of component A may consist of another aromatic dicarboxylic acid such as terephthalic acid, --- isophthalic acid,-1,5-, 2,6- and 2,7-naphthalene-dicarboxylic acid and trans-4,4'-stilbenedicarboxylic - 4 - 201663i acid. Preferably, 100 mole percent of dicarboxylic acid component A consists of 4,4'-biphenyldicarboxylic acid residues.
A portion, e.g., up to 10 mole percent, of diol component B may consist of residues derived from diols other than ethylene glycol and 1,4-butanediol.
Examples of such diols include alXylene glycols containing 3 to 8 carbon atoms such as 1,2- and 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexane-dimethanol (cis, trans or mixed isomers) and the like and bis-hydroxyalkylbenzene compounds such as p-xylylene glycol and mixtures thereof.
Normally, 100 mole percent of diol component B will consist of a combination of only the residues of ethylene glycol and 1,4-butanediol. The mole ratio of the ethylene glycol residues to 1,4-butanediol residues may be in the range of 3:1 to 0.45:1, with the range of 3:1 to 1.5:1 being particularly preferred. Thus, when the diol residues of our novei polyesters consist only of residues of ethylene glycol and 1,4-butanediol, 25 to 70 mole percent, preferably 25 to 40 mole percent, of the diol residues consist of 1,4-butanediol residues.
The polyesters of our invention which are especially preferred have an inherent viscosity of at least 0.8 dl~g and consist of at least 95 mole percent of components A and B as defined hereinabove.
The most preferred polyesters consist only of components A and B.
Our novel polyes.e-s and the synthesis thereof are further illustrated by the following examples.
PROCEDURE
The polyesters were prepared by reacting dimethyl 4,4'-biphenyldicarboxylate with varying amounts of ethylene glycol and 1,4-butanediol in the presence of titanium tetraisopropoxide at elevated temperatures using reduced pressures for the final polycondensation. The apparatus employed consisted of a 1-L flas~ e~uipped WO90/1~27 PCT/US90/010~
^`- 2046G~4~`~
with an inlet for nitPogen, a metal stirrer and a short distillation column. Thus, in Example 1, 216.0 g (0.80 mole) dimethyl 4,4'-biphenyldicarboxylate, 148.8 g (2.40 moles) ethylene glycol, 35.0 g (0.40 mole) 1,4-butane-diol and 0.15 g titanium tetraisopropoxide were heatedat 190C for 3 hours and at 220C for 1 hour and then the temperature was raised to 300C for 10 minutes. A
vacuum of 0.067 kPa (0.5 mm Hg) was applied gradually over the next 5 minutes and a full vacuum was maintained at a temperature of 300C for 18 minutes.
The white, crystalline polymer was allowed to solidify in the flask and then was reheated to pull the polymer away from the glass flask. The polymer was allo~ed to solidify again and was recovered by breaking the flask and chiseling it from the stirrer. In Examples 6 and 7 and Comparative Examples C-1, C-2 and C-3, the polyesters solidified in the melt during their preparation. The solidified polymers were ground to pass a 3-mm screen and t~e ground p~lymers were solid state polymerized at 100C for 1 hour and then at 230C
for 3 hours.
The content of the diol residues, determined by proton nuclear magnetic resonance spectroscopy, and the inherent viscosities (I.V., dl/g), determined at 25C
using 0.1 g of polyester per 100 mL of a solvent consisting of 25 parts by weight phenol, 35 parts by weight tetrachloroethane and 40 parts by weight p-chlorophenol, of the polyesters prepared in Examples 1-7 and Comparative Examples C-1, C-2 and C-3 are set forth in Table I. Diol residue contents are given as mole percent ethylene glycol residues (EG) and mole percent 1,4-butanediol residues (BD). The ~ polyester of Comparative Example 1 was prepared from only dimethyl 4,4'-biphenyldicarboxylate and 1,4-butanediol.
~ .
The polyesters of the above examples were ground to pass a 3-mm screen, dried at 100C in a vacuum oven for ~4 hours and injection-molded into 1.6 mm-thick ASTM Type L tensile bars and 12.7 x 127 x 3.2 mm-s thick flexure bars using a 28.35-g Watson-Stillman plunger-type molding machine. The tensile strength (103 psi, ASTM D638), flexural modulus tlO5 psi, ASTM
D790) and the heat deflection temperature (HDT, C at 264 psi stress) were determined for each of the polyesters and the values are set forth in Table II.
The inherent viscosities (I.V., dl~g) for the polyesters of Examples 1-5 and Comparative Example C-1 after molding also are set forth in Table II. The molding temperature (C) given in Table II for each polyester is the temperature of the nozzle on the molding machine. The barrel temperature of the molding machine is about 15C above the nozzle temperature. Due to its high melting temperature, the polyester of Comparative Example C-1 was molded with difficulty.
TABLE I
Example EG BD I.V.
1 71 29 0.87 2 73 27 1.05 3 65 35 0.95 4 63 37 0.84 63 37 0.89 6 55 45 1.43 7 50 50 1.17 C-l 0 100 1.27 C-2 79 21 1.02 C-3 27 73 1.11 TABLE II
Molding Tensile Flexural Example TemP. I.V. Strength HDT Modulus 1 295 0.83 21.9 236 12.2 2 310 0.92 39.5 234 12.8 3 290 0.87 31.2 235 14.7 4 300 0.80 28.0 233 13.1 310 0.74 23.5 234 12.0 6 320 - 27.6 225 11.5 7 310 - 24.1 215 10.4 C-l 330 1.20 9.8 222 4.4 C-2 330 - 13.5 210 6.6 C-3 320 - 18.4 191 5.8 The polyesters of our invention also exhibit excellent resistance to solvents and chemicals. Molded bars are substantially unaffected after exposure for 24 hours in a variety of solvents and chemicals such as toluene, methylene chloride, 1,2-dichloroethane, acetone, 3-methyl-2-butanone, acetic acid, ethyl acetate, ethanol, water, 50~50 water~ethanol, benzyl alcohol, sulfuric acid, nitric acid, 10 percent aqueous sodium hydroxide, gasoline and 5% laundry bleach tClorox (trademark)].
. .
'~' 20~634 Our novel polyesters may be blended or compounded with a wide variety of other polymeric materials to provide molding and extrusion compositions useful in the manufacture of articles having a desirable combination of properties. For example, such compositions may contain about 10 to 90 weight percent of one of our novel polyesters and about 90 to 10 weight percent of one or more other polymeric materials. Suitable polymeric materials include nylon 6,6, poly(ether-imides) such as Ultem (trademark) poly(ether-imide) available from General Electric, poly(phenylene oxides) such as poly(2,6-dimethylphenylene oxide) and poly-(phenylene oxide), poly(phenylene oxide)~polystyrene blends such as Noryl (trademark) resins available ~rom General Electric, polyesters, poly(phenylene sulfides), poly(phenylene sulfide~sulfones), poly(ester-carbonates), polycarbonates such as Lexan (trademark) polycarbonate available from General Electric, polysulfones, poly(ether-sulfones) such as those derived from the aromatic dihydroxy compounds disclosed in U.S.
Patents 3,030,335 and 3,317,466.
The polyesters of this invention and blends thereof with other polymeric materials may contain additives commonly employed in polymers including flame retardants such as phosphorus, halogen compounds and halogen compounds in combination with antimony compounds, pigments, stabilizers, fillers such as talc and mica, and reinforcing agents such as glass fiber, Kevlar (trademark) aramid [poly(p-phenylene terephthalamide)]
fibers and carbon fiber.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
'~L
ACID, 1,4-BUTANEDIOL AND ETHYLENE GLYCOL
This invention concerns certain novel, melt-processable~poIyesters comprised primarily of residues of 4,4'-biphenyldicarboxylic acid, ethylene glycol and 1,4-butanediol. Articles injection-molded from the polyesters exhibit a unique combination of properties including unusually high tensile strength, heat resistance, and flexural modulus and excellent resistance to chemicals and solvents.
Polyesters derived from 4,4'-biphenyldicarboxylic acid and various aliphatic diols have been described generally in the literature. Polyesters comprised of residues of 4,4'-biphenyldicarboxylic acid, ethylene glycol, 1,4-butanediol and 1,6-hexanediol are disclosed by Meurisse et al, in the British Polymer Journal, 13, 57 (1981). Jackson and Morris reviewed polyesters comprised of residues of 4,4'-biphenyldicarboxylic acid and various aliphatic diols in the Journal of Applied Polymer Science, Applied Polymer Symposia, 41, 307-326 (1985). Krigbaum et al, Journal of Applied Polymer Science, Polymer Letters Edition, 20, 109-115 (1982) disclose relatively low molecular weight polyesters comprised of 4,4'-biphenyldicarboxylic acid residues -and residues derived from one of several aliphatic diols.
Polyesters containing residues of 4,4'-biphenyl-dicarboxylic acid also are disclosèd in Macromolecules, 21(1), 278-280 (1988); Polymer, 24(10), 1299-1307 (1983); Japanese Published Patent Applications (Kokai) 61-236,821 and 57-198,726; Kobunshi Ronbunshu, 44(12), 983-986 (December 1987) and U.S. Patents 2,967,266, 3,842,040, and 3,842,041. German Offenlegungsschrift 1,935,252 discloses polyesters comprised of the residues of at least two diacids such as terephthalic acid and WO ~11~27 PCT/US~/01~
2û~6~
4,4'-biphenyldicarboxylic acid and two diols such as ethylene glycol and 1,4-cyclohexanedimethanol. These known polyesters typically have inherent viscosities less than 1.2 and contain 4,4'-biphenyldicarboxylic S acid residues and usually residues of at least one additional diacid and residues of at least two diols.
U.S. Patent 4,742,151 describes generally ultra-high molecular weight polyesters having inherent viscosities greater than 1.5 comprised of diacid residues of aromatic dicarboxylic acids and diol residues of alkylene glycols of 2 to 6 carbon atoms.
The polyesters of the present invention have an inherent viscosity of at least 0.6 dl/g determined at 25C using 0.1 g of polyester per 100 mL of a solvent consisting of 25 parts by weight phenol, 35 parts by weight tetrachloroethane and 40 parts by weight p-chlorophenol and contain the following components:
A. dicarboxylic acid residues consisting of at least 80 mole percent of residues having the structure:
~ C-B. diol residues consisting of at least 90 mole percent of residues having the structure:
(1) -OCH2CH2O- and (2) -OCH2CH2CH2CH2O- and, optionally, C. dicarboxylic acid and/or diol residues, i.e., dicarboxylic acid residues, diol residues or mixtures thereof, other than components A and B, wherein the mole ratio of B(l):B(2) is about 3:1 to 0.45:1. The mole percent values set forth above are based on a total of dicarboxylic acid and diol residues of 200 percent in which the mole ratio of dicarboxylic acid residues to diol residues is 1:1, i.e., alternating repeating units of diacid and diol residues.
WO ~/1~27 PCT/US~/01~4 - 20~663~
Articles injection-molded from the polyesters of our invention possess a unique combination of high tensile strength, heat resistance, and flexural modulus.
For example, an article injection-molded from a polyester consisting only of 4,4'-biphenyldicarboxylic acid and 1,4-butanediol residues gave a tensile strength of approximately 67,571 kPa (9,800 psi). The polyester consisting only of 4,4'-biphenyldicarboxylic acid and ethylene glycol residues melts at such a high tempera-ture that it cannot be molded without encounteringsevere decomposition problems. We have found that certain of the polyesters provided by this invention can be prepared in the melt and that articles injection-molded therefrom exhibit a 2- to 3-fold increase in tensile strength, e.g., ASTM D638 tensile strengths in the range of 137,900 to 206,850 kPa (20,000 to 30,000 psi), when compared to polyester derived only from 4,4'-biphenyldicarboxylic acid and 1,4-butanediol.
The polyesters of this invention are prepared by methods generally known in the art for preparing high molecular weight polyesters by polymerizing one or more dicarboxylic acids and two or more diols, as specified hereinabove. The polyesters may be produced by direct condensation or ester interchange in the melt or in the solid phase or by a combination of these processes.
The 4,4'-biphenyldicarboxylic acid residues may be derived from the free acid or from esters such as dimethyl, diethyl, dibutyl, diphenyl, di(2-~hydroxy-ethyl)- or di(4-hydroxybutyl)-4,4'-biphenyldicarboxylate or mixtures of such esters. Up to 20 mole percent, preferably up to 10 mole percent, of the dicarboxylic acid residues of component A may consist of another aromatic dicarboxylic acid such as terephthalic acid, --- isophthalic acid,-1,5-, 2,6- and 2,7-naphthalene-dicarboxylic acid and trans-4,4'-stilbenedicarboxylic - 4 - 201663i acid. Preferably, 100 mole percent of dicarboxylic acid component A consists of 4,4'-biphenyldicarboxylic acid residues.
A portion, e.g., up to 10 mole percent, of diol component B may consist of residues derived from diols other than ethylene glycol and 1,4-butanediol.
Examples of such diols include alXylene glycols containing 3 to 8 carbon atoms such as 1,2- and 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexane-dimethanol (cis, trans or mixed isomers) and the like and bis-hydroxyalkylbenzene compounds such as p-xylylene glycol and mixtures thereof.
Normally, 100 mole percent of diol component B will consist of a combination of only the residues of ethylene glycol and 1,4-butanediol. The mole ratio of the ethylene glycol residues to 1,4-butanediol residues may be in the range of 3:1 to 0.45:1, with the range of 3:1 to 1.5:1 being particularly preferred. Thus, when the diol residues of our novei polyesters consist only of residues of ethylene glycol and 1,4-butanediol, 25 to 70 mole percent, preferably 25 to 40 mole percent, of the diol residues consist of 1,4-butanediol residues.
The polyesters of our invention which are especially preferred have an inherent viscosity of at least 0.8 dl~g and consist of at least 95 mole percent of components A and B as defined hereinabove.
The most preferred polyesters consist only of components A and B.
Our novel polyes.e-s and the synthesis thereof are further illustrated by the following examples.
PROCEDURE
The polyesters were prepared by reacting dimethyl 4,4'-biphenyldicarboxylate with varying amounts of ethylene glycol and 1,4-butanediol in the presence of titanium tetraisopropoxide at elevated temperatures using reduced pressures for the final polycondensation. The apparatus employed consisted of a 1-L flas~ e~uipped WO90/1~27 PCT/US90/010~
^`- 2046G~4~`~
with an inlet for nitPogen, a metal stirrer and a short distillation column. Thus, in Example 1, 216.0 g (0.80 mole) dimethyl 4,4'-biphenyldicarboxylate, 148.8 g (2.40 moles) ethylene glycol, 35.0 g (0.40 mole) 1,4-butane-diol and 0.15 g titanium tetraisopropoxide were heatedat 190C for 3 hours and at 220C for 1 hour and then the temperature was raised to 300C for 10 minutes. A
vacuum of 0.067 kPa (0.5 mm Hg) was applied gradually over the next 5 minutes and a full vacuum was maintained at a temperature of 300C for 18 minutes.
The white, crystalline polymer was allowed to solidify in the flask and then was reheated to pull the polymer away from the glass flask. The polymer was allo~ed to solidify again and was recovered by breaking the flask and chiseling it from the stirrer. In Examples 6 and 7 and Comparative Examples C-1, C-2 and C-3, the polyesters solidified in the melt during their preparation. The solidified polymers were ground to pass a 3-mm screen and t~e ground p~lymers were solid state polymerized at 100C for 1 hour and then at 230C
for 3 hours.
The content of the diol residues, determined by proton nuclear magnetic resonance spectroscopy, and the inherent viscosities (I.V., dl/g), determined at 25C
using 0.1 g of polyester per 100 mL of a solvent consisting of 25 parts by weight phenol, 35 parts by weight tetrachloroethane and 40 parts by weight p-chlorophenol, of the polyesters prepared in Examples 1-7 and Comparative Examples C-1, C-2 and C-3 are set forth in Table I. Diol residue contents are given as mole percent ethylene glycol residues (EG) and mole percent 1,4-butanediol residues (BD). The ~ polyester of Comparative Example 1 was prepared from only dimethyl 4,4'-biphenyldicarboxylate and 1,4-butanediol.
~ .
The polyesters of the above examples were ground to pass a 3-mm screen, dried at 100C in a vacuum oven for ~4 hours and injection-molded into 1.6 mm-thick ASTM Type L tensile bars and 12.7 x 127 x 3.2 mm-s thick flexure bars using a 28.35-g Watson-Stillman plunger-type molding machine. The tensile strength (103 psi, ASTM D638), flexural modulus tlO5 psi, ASTM
D790) and the heat deflection temperature (HDT, C at 264 psi stress) were determined for each of the polyesters and the values are set forth in Table II.
The inherent viscosities (I.V., dl~g) for the polyesters of Examples 1-5 and Comparative Example C-1 after molding also are set forth in Table II. The molding temperature (C) given in Table II for each polyester is the temperature of the nozzle on the molding machine. The barrel temperature of the molding machine is about 15C above the nozzle temperature. Due to its high melting temperature, the polyester of Comparative Example C-1 was molded with difficulty.
TABLE I
Example EG BD I.V.
1 71 29 0.87 2 73 27 1.05 3 65 35 0.95 4 63 37 0.84 63 37 0.89 6 55 45 1.43 7 50 50 1.17 C-l 0 100 1.27 C-2 79 21 1.02 C-3 27 73 1.11 TABLE II
Molding Tensile Flexural Example TemP. I.V. Strength HDT Modulus 1 295 0.83 21.9 236 12.2 2 310 0.92 39.5 234 12.8 3 290 0.87 31.2 235 14.7 4 300 0.80 28.0 233 13.1 310 0.74 23.5 234 12.0 6 320 - 27.6 225 11.5 7 310 - 24.1 215 10.4 C-l 330 1.20 9.8 222 4.4 C-2 330 - 13.5 210 6.6 C-3 320 - 18.4 191 5.8 The polyesters of our invention also exhibit excellent resistance to solvents and chemicals. Molded bars are substantially unaffected after exposure for 24 hours in a variety of solvents and chemicals such as toluene, methylene chloride, 1,2-dichloroethane, acetone, 3-methyl-2-butanone, acetic acid, ethyl acetate, ethanol, water, 50~50 water~ethanol, benzyl alcohol, sulfuric acid, nitric acid, 10 percent aqueous sodium hydroxide, gasoline and 5% laundry bleach tClorox (trademark)].
. .
'~' 20~634 Our novel polyesters may be blended or compounded with a wide variety of other polymeric materials to provide molding and extrusion compositions useful in the manufacture of articles having a desirable combination of properties. For example, such compositions may contain about 10 to 90 weight percent of one of our novel polyesters and about 90 to 10 weight percent of one or more other polymeric materials. Suitable polymeric materials include nylon 6,6, poly(ether-imides) such as Ultem (trademark) poly(ether-imide) available from General Electric, poly(phenylene oxides) such as poly(2,6-dimethylphenylene oxide) and poly-(phenylene oxide), poly(phenylene oxide)~polystyrene blends such as Noryl (trademark) resins available ~rom General Electric, polyesters, poly(phenylene sulfides), poly(phenylene sulfide~sulfones), poly(ester-carbonates), polycarbonates such as Lexan (trademark) polycarbonate available from General Electric, polysulfones, poly(ether-sulfones) such as those derived from the aromatic dihydroxy compounds disclosed in U.S.
Patents 3,030,335 and 3,317,466.
The polyesters of this invention and blends thereof with other polymeric materials may contain additives commonly employed in polymers including flame retardants such as phosphorus, halogen compounds and halogen compounds in combination with antimony compounds, pigments, stabilizers, fillers such as talc and mica, and reinforcing agents such as glass fiber, Kevlar (trademark) aramid [poly(p-phenylene terephthalamide)]
fibers and carbon fiber.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
'~L
Claims (12)
1. A polyester having an inherent viscosity of at least 0.6 dl/g determined at 25°C using 0.1 g of polyester per 100 mL of a solvent consisting of 25 parts by weight phenol, 35 parts by weight tetrachloroethane and 40 parts by weight p-chlorophenol and containing the following components:
A. dicarboxylic acid residues consisting of at least 80 mole percent of residues having the structure:
B. diol residues consisting of at least 90 mole percent of residues having the structure:
(1) -OCH2CH2O- and (2) -OCH2CH2CH2CH2O- and, optionally, C. dicarboxylic acid and/or diol residues other than components A and B;
wherein the mole ratio of components B(1):B(2) is 3:1 to 0.45:1.
A. dicarboxylic acid residues consisting of at least 80 mole percent of residues having the structure:
B. diol residues consisting of at least 90 mole percent of residues having the structure:
(1) -OCH2CH2O- and (2) -OCH2CH2CH2CH2O- and, optionally, C. dicarboxylic acid and/or diol residues other than components A and B;
wherein the mole ratio of components B(1):B(2) is 3:1 to 0.45:1.
2. A polyester according to Claim 1 having an inherent viscosity of at least 0.8 dl/g and wherein the mole ratio of components B(1):B(2) is 3:1 to 1.5:1.
3. A polyester according to Claim 1 having an inherent viscosity of at least 0.8 dl/g, wherein component C
is selected from residues of terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, trans-4,4'-stilbenedicarboxylic acid, alkylene glycols containing 3 to 8 carbon atoms, 1,4-cyclohexanedimethanol, p-xylylene glycol or mixtures thereof and the mole ratio of components B(1):B(2) is 3:1 to 1.5:1.
is selected from residues of terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, trans-4,4'-stilbenedicarboxylic acid, alkylene glycols containing 3 to 8 carbon atoms, 1,4-cyclohexanedimethanol, p-xylylene glycol or mixtures thereof and the mole ratio of components B(1):B(2) is 3:1 to 1.5:1.
4. A polyester having an inherent viscosity of at least 0.8 dl/g determined at 25°C using 0.1 g of polyester per 100 mL of a solvent consisting of 25 parts by weight phenol, 35 parts by weight tetrachloroethane and 40 parts by weight p-chlorophenol and containing the following components:
A. dicarboxylic acid residues consisting at least 90 mole percent of residues having the structure:
B. diol residues consisting of at least 90 mole percent of residues having the structure:
(1) -OCH2CH2O- and (2) -OCH2CH2CH2CH2O- and, optionally, C. dicarboxylic acid and/or diol residues other than components A and B;
wherein the mole ratio of components B(1):B(2) is 3:1 to 1.5:1.
A. dicarboxylic acid residues consisting at least 90 mole percent of residues having the structure:
B. diol residues consisting of at least 90 mole percent of residues having the structure:
(1) -OCH2CH2O- and (2) -OCH2CH2CH2CH2O- and, optionally, C. dicarboxylic acid and/or diol residues other than components A and B;
wherein the mole ratio of components B(1):B(2) is 3:1 to 1.5:1.
5. A polyester according to Claim 4 wherein component C is selected from residues of terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, trans-4,4'-stilbenedicarboxylic acid, alkylene glycols containing 3 to 8 carbon atoms, 1,4-cyclohexanedimethanol, p-xylylene glycol or mixtures thereof.
6. A polyester having an inherent viscosity of at least 0.8 dl/g determined at 25°C using 0.1 g of polyester per 100 mL of a solvent consisting of 25 parts by weight phenol, 35 parts by weight tetrachloroethane and 40 parts by weight p-chlorophenol and consisting essentially of the following components:
A. dicarboxylic acid residues having the structure:
and B. diol residues having the structure:
(1) -OCH2CH2O- and (2) -OCH2CH2CH2CH2O-;
wherein the mole ratio of components B(1):B(2) is 3:1 to 0.45:1.
A. dicarboxylic acid residues having the structure:
and B. diol residues having the structure:
(1) -OCH2CH2O- and (2) -OCH2CH2CH2CH2O-;
wherein the mole ratio of components B(1):B(2) is 3:1 to 0.45:1.
7. A polyester according to Claim 6 wherein the mole ratio of components B(1):B(2) is 3:1 to 1.5:1.
8. A shaped article of the polyester of Claim 1.
9. An article according to Claim 8 which has been formed by injection-molding.
10. A shaped article of the polyester of Claim 6.
11. An article according to Claim 10 which has been formed by injection-molding.
12. The polyester of Claim 1 containing a reinforcing amount of glass fiber, poly(p-phenylene terephthalamide) fiber or carbon fiber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US315,649 | 1989-02-27 | ||
| US07/315,649 US5081220A (en) | 1989-02-27 | 1989-02-27 | Copolyesters of 4,4'-biphenyldicarboxylic acid, 1,4-butanediol and ethylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2046634A1 CA2046634A1 (en) | 1990-08-28 |
| CA2046634C true CA2046634C (en) | 1996-08-13 |
Family
ID=23225423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002046634A Expired - Fee Related CA2046634C (en) | 1989-02-27 | 1990-02-22 | Copolyesters of 4,4'-biphenyldicarboxylic acid, 1, 4-butanediol and ethylene glycol |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5081220A (en) |
| EP (2) | EP0389385B1 (en) |
| JP (1) | JPH04503689A (en) |
| KR (2) | KR0149673B1 (en) |
| AT (1) | ATE98968T1 (en) |
| CA (1) | CA2046634C (en) |
| DE (1) | DE69005339T2 (en) |
| DK (1) | DK0389385T3 (en) |
| ES (1) | ES2060991T3 (en) |
| WO (1) | WO1990010027A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2928422B2 (en) * | 1991-05-10 | 1999-08-03 | ポリプラスチックス株式会社 | Heat resistant polyester resin and resin composition |
| CA2113639A1 (en) * | 1991-07-25 | 1993-02-04 | Eui W. Choe | Copolyesters for high modulus fibers |
| US5138022A (en) * | 1991-08-01 | 1992-08-11 | The Dow Chemical Company | Thermoplastic polyesters containing biphenylene linkages |
| US5128185A (en) * | 1991-08-29 | 1992-07-07 | E. I. Du Pont De Nemours And Company | Copolyetherester elastomer with poly(1,3-propylenebibenzoate) hard segment |
| DE59308819D1 (en) * | 1992-07-22 | 1998-09-03 | Hoechst Ag | Biaxially oriented film containing layers of polyethylene naphthalate bibenzoate (PENBB), process for producing these films and use thereof |
| EP0671990A1 (en) * | 1992-12-09 | 1995-09-20 | Hoechst Aktiengesellschaft | Biaxially oriented copolyester film for capacitor dielectric use or thermal transfer ribbon use |
| EP0608991B1 (en) * | 1993-01-27 | 1997-05-21 | Nippon Oil Co. Ltd. | Liquid crystalline polyesters |
| US20070037960A1 (en) * | 2005-08-15 | 2007-02-15 | General Electric Company | Copolyester stilbene embossed film and methods of making the same |
| US7105627B1 (en) * | 2005-08-15 | 2006-09-12 | General Electric Company | Polyester stilbene composition |
| US9477011B2 (en) | 2010-06-30 | 2016-10-25 | Yufeng Liu | Multilayer optical film |
| WO2012005879A1 (en) | 2010-06-30 | 2012-01-12 | 3M Innovative Properties Company | Optical stack having birefringent layer of optically symmetrical crystallites |
| JP5502023B2 (en) | 2010-09-03 | 2014-05-28 | 日東電工株式会社 | Method for producing optical film laminate roll having polarizing film |
| JP5701679B2 (en) | 2010-09-03 | 2015-04-15 | 日東電工株式会社 | Method and apparatus for sequentially attaching optical films having polarizing films on rectangular panels |
| JP5511730B2 (en) | 2010-09-03 | 2014-06-04 | 日東電工株式会社 | Continuous manufacturing method and apparatus for optical panel assembly |
| JP5478553B2 (en) | 2010-09-03 | 2014-04-23 | 日東電工株式会社 | Continuous web-like optical film laminate roll and method for producing the same |
| US10767005B2 (en) | 2015-12-22 | 2020-09-08 | Exxonmobil Chemical Patents Inc. | Bibenzoate copolyesters and methods to produce them |
| US10287402B2 (en) | 2016-04-29 | 2019-05-14 | Exxonmobil Chemical Patents Inc. | Polycarbonate-polyolefin block copolymers and methods of making them |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1181102A (en) * | 1956-08-17 | 1959-06-11 | American Viscose Corp | Polyesters manufacturing processes and resulting products |
| US2976266A (en) * | 1957-10-17 | 1961-03-21 | American Viscose Corp | Film-forming polyesters of bibenzoic acid |
| US3909489A (en) * | 1973-11-07 | 1975-09-30 | Goodyear Tire & Rubber | Polyesters and copolyesters having improved flame retardancy |
| US4728717A (en) * | 1987-01-02 | 1988-03-01 | Eastman Kodak Company | Polyesters of trans-4,4'-stilbenedicarboxylic acid, 1,4-cyclohexanedimethanol and 1,4-butanediol |
-
1989
- 1989-02-27 US US07/315,649 patent/US5081220A/en not_active Expired - Lifetime
-
1990
- 1990-02-22 EP EP90420094A patent/EP0389385B1/en not_active Expired - Lifetime
- 1990-02-22 EP EP90904499A patent/EP0460095A1/en active Pending
- 1990-02-22 WO PCT/US1990/001094 patent/WO1990010027A1/en not_active Application Discontinuation
- 1990-02-22 DK DK90420094.6T patent/DK0389385T3/en active
- 1990-02-22 KR KR1019910700995A patent/KR0149673B1/en not_active IP Right Cessation
- 1990-02-22 AT AT90420094T patent/ATE98968T1/en not_active IP Right Cessation
- 1990-02-22 ES ES90420094T patent/ES2060991T3/en not_active Expired - Lifetime
- 1990-02-22 DE DE69005339T patent/DE69005339T2/en not_active Expired - Fee Related
- 1990-02-22 JP JP2504462A patent/JPH04503689A/en active Pending
- 1990-02-22 KR KR1019980700314A patent/KR0153749B1/en not_active IP Right Cessation
- 1990-02-22 CA CA002046634A patent/CA2046634C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0460095A1 (en) | 1991-12-11 |
| JPH04503689A (en) | 1992-07-02 |
| KR0149673B1 (en) | 1998-10-15 |
| DK0389385T3 (en) | 1994-01-31 |
| US5081220A (en) | 1992-01-14 |
| KR0153749B1 (en) | 1998-12-01 |
| WO1990010027A1 (en) | 1990-09-07 |
| DE69005339D1 (en) | 1994-02-03 |
| DE69005339T2 (en) | 1994-07-14 |
| KR920701300A (en) | 1992-08-11 |
| ES2060991T3 (en) | 1994-12-01 |
| CA2046634A1 (en) | 1990-08-28 |
| ATE98968T1 (en) | 1994-01-15 |
| EP0389385A1 (en) | 1990-09-26 |
| EP0389385B1 (en) | 1993-12-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |